CN103746147A - Positive pole container of sodium sulfur battery - Google Patents
Positive pole container of sodium sulfur battery Download PDFInfo
- Publication number
- CN103746147A CN103746147A CN201310669116.XA CN201310669116A CN103746147A CN 103746147 A CN103746147 A CN 103746147A CN 201310669116 A CN201310669116 A CN 201310669116A CN 103746147 A CN103746147 A CN 103746147A
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- China
- Prior art keywords
- carbon
- aluminium
- sodium
- container
- sulphur battery
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- BNOODXBBXFZASF-UHFFFAOYSA-N [Na].[S] Chemical compound [Na].[S] BNOODXBBXFZASF-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 239000002131 composite material Substances 0.000 claims abstract description 36
- RQMIWLMVTCKXAQ-UHFFFAOYSA-N [AlH3].[C] Chemical compound [AlH3].[C] RQMIWLMVTCKXAQ-UHFFFAOYSA-N 0.000 claims abstract description 28
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 11
- 239000004411 aluminium Substances 0.000 claims description 26
- 229910052782 aluminium Inorganic materials 0.000 claims description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 21
- 229910052799 carbon Inorganic materials 0.000 claims description 17
- 239000000843 powder Substances 0.000 claims description 12
- 239000007767 bonding agent Substances 0.000 claims description 9
- 229910000838 Al alloy Inorganic materials 0.000 claims description 7
- 239000000428 dust Substances 0.000 claims description 7
- 239000010935 stainless steel Substances 0.000 claims description 7
- 229910001220 stainless steel Inorganic materials 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 6
- 229910001209 Low-carbon steel Inorganic materials 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 230000007797 corrosion Effects 0.000 abstract description 8
- 238000005260 corrosion Methods 0.000 abstract description 8
- 238000000034 method Methods 0.000 description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- HYHCSLBZRBJJCH-UHFFFAOYSA-N sodium polysulfide Chemical compound [Na+].S HYHCSLBZRBJJCH-UHFFFAOYSA-N 0.000 description 7
- 239000005864 Sulphur Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- 239000006229 carbon black Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- 238000005422 blasting Methods 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000007731 hot pressing Methods 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 238000009628 steelmaking Methods 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000007751 thermal spraying Methods 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
- H01M10/39—Accumulators not provided for in groups H01M10/05-H01M10/34 working at high temperature
- H01M10/3909—Sodium-sulfur cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
- H01M10/39—Accumulators not provided for in groups H01M10/05-H01M10/34 working at high temperature
- H01M10/3909—Sodium-sulfur cells
- H01M10/3954—Sodium-sulfur cells containing additives or special arrangement in the sulfur compartment
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Secondary Cells (AREA)
Abstract
The invention relates to a positive pole container of a sodium sulfur battery, the positive pole container comprises a container casing made of a metal, the inner wall of the container casing is provided with an inner liner of a continuous aluminum carbon composite material, the container casing is a cylindrical structure with one end open and the other end closed, the continuous aluminum carbon composite material comprises 30-90wt.% of metal aluminum powder and the balance of carbon material, the inner liner of the continuous aluminum carbon composite material of the positive pole container has good corrosion resistance and electrical conductivity, and is helpful to improve the safety and service life of the sodium sulfur battery.
Description
Technical field
The present invention relates to energy storage technology field, relate more specifically to a kind of anodal container of sodium-sulphur battery.
Background technology
Sodium-sulphur battery is take sodium ion conductor beta – aluminium oxide as electrolyte is as solid electrolyte, and respectively take SODIUM METAL and sulphur as negative pole and anodal secondary cell.Sodium-sulphur battery has enjoyed countries in the world to pay close attention to since being invented by U.S. Ford from 1967 in recent decades, is regarded as a kind of energy-storage battery of high-energy-density.Sodium-sulphur battery has broad application prospects in energy storage technology field and huge market potential.
Liquid sulfur in the positive electrode of sodium-sulphur battery and sodium polysulfide (Na
2s
x ) there is severe corrosive, can cause anodal container to be corroded, be the main cause that causes cell performance degradation.The anodal container of sodium-sulphur battery generally adopts stainless steel, metallic aluminium or aluminum alloy materials at present.The anodal container of stainless steel has good hot properties, but the corrosivity of its anti-sodium polysulfide is very poor.The corrosivity of the anti-sulphur of metallic aluminium and sodium polysulfide is very strong, but it easily forms the Al of one deck insulation on surface
2s
3fine and close diaphragm, the therefore sharply rising of the internal resistance of cell, thus affect the serviceability of battery.Crome metal is lower in the corrosion rate of sulphur and sodium polysulfide, and chromium plating film is considered to a kind of effectively means of defence, and its preparation method has the methods such as plating, vapour deposition and spraying, but it is very difficult to obtain the dense coating that cohesive force is good.Japan Patent [JP2005071902A] has been announced a kind of by obtain the method for fine and close containing metal chrome coating in anodal container inner wall thermal spraying, but the method container must be made siphunculus form, this often causes container bottom (the cylinder end) and chamber wall (cylindrical shell) junction surface to become etch-proof weakness zone the most, thereby in use brings potential safety hazard to battery.
Metallic aluminium itself has excellent corrosion resistance, is only the Al generating
2s
3increased the internal resistance of cell.Therefore; if the anodal container of sodium-sulphur battery can utilize the anti-corrosive properties of metallic aluminium excellence; can overcome again the problem that the internal resistance of cell increases after metallic aluminium of using; can also form continuous overcoat outer cover metal is carried out to general protection; can greatly improve the coefficient of safety that sodium-sulphur battery is used, promote sodium-sulphur battery and be applied to more wide field.The present invention adopts aluminium carbon composite protective lining to achieve the above object, and correlation technique has no report.
Summary of the invention
In order to overcome the defect of above-mentioned prior art, the present invention aims to provide the anodal container of the sodium-sulphur battery of a kind of Corrosion Protection excellence and good conductivity, the fail safe of using to improve sodium-sulphur battery.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is:
An anodal container for sodium-sulphur battery, comprises the shell of tank that metal is made, and it is characterized in that: the inwall of described shell of tank is prepared the liner of the continuous aluminium carbon composite of one deck.
Described shell of tank is the tubular structure of an end opening, other end sealing, and described shell of tank is the one in aluminium, aluminium alloy, mild steel and stainless steel.
Described aluminium carbon composite comprises metallic aluminium powder and carbon materials, and wherein metallic aluminium powder is 30～90wt.%, and all the other are carbon materials.
Described carbon materials comprises carbon dust (at least one in graphite powder and carbon black) and bonding agent carbon (for the product after bonding agent carbonization), 50～100wt.% that wherein carbon dust is carbon materials, and all the other are bonding agent carbon.
The liner of described aluminium carbon composite can be prepared by common process, static pressure or the spray mo(u)lding such as can adopt, then obtains finished product through Overheating Treatment, after also can raw material mixing, directly through hot pressing, obtains finished product.
Metallic aluminium particle in the liner of described aluminium carbon composite forms the main body framework of composite material, and described carbon materials forms the conductive network being interconnected.
The present invention has the following advantages:
1, the present invention adopts aluminium carbon composite as liner, has both possessed excellent anti-liquid sulfur and the sodium polysulfide corrosive nature of metallic aluminium, possesses again good conductivity (utilizing material with carbon element to form continuous conduction network), can effectively avoid metallic aluminium Surface Creation Al
2s
3the problem of bringing the internal resistance of cell to increase.The aluminium carbon composite liner of the anodal container of this sodium-sulphur battery has both good Corrosion Protection and electric conductivity simultaneously, is conducive to improve sodium-sulphur battery fail safe and useful life.
2, shell of tank of the present invention is the tubular structure of an end opening, other end sealing, at container inner wall, forms continuous, seamless aluminium carbon composite liner, has avoided prior art problem, the problem includes: container bottom and the poor problem of chamber wall joint portion barrier propterty.
3, in the present invention, aluminium carbon composite consists of metallic aluminium powder and carbon materials, and its raw material sources are abundant, price is low, and its preparation method can adopt common process to realize in addition, has avoided high investment that prior art adopts and expensive hot-spraying technique.
Accompanying drawing explanation
Fig. 1 is the generalized section of the anodal container of sodium-sulphur battery of the present invention.
Fig. 2 is the microstructure schematic diagram of aluminium carbon composite liner of the present invention.
Mark in figure: 1 shell of tank, 2 liners, 3 metallic aluminium particles, 4 conductive networks.
Embodiment
Below in conjunction with specific embodiment, the present invention is further elaborated, but the present invention is not limited to following examples, and described method is conventional method if no special instructions, and described material all can obtain from open commercial sources if no special instructions.
As shown in Figure 1, a kind of anodal container of sodium-sulphur battery, comprise the shell of tank 1 that metal is made, shell 1 is aluminium alloy making, the inwall of shell of tank prepare one deck continuously, equal liners 2 of even seamless aluminium carbon composite, this aluminium carbon composite is containing metallic aluminium powder, the carbon materials of 32wt.%, wherein the bonding agent carbon of graphite powder (being carbon dust) 30wt.% and 2wt.% of 68wt.%.Its preparation method is: get the aluminium alloy cylinder (concrete size is determined according to battery capacity size) of remaining silent in end opening, an one end, aluminium alloy cylinder inwall is first through cleaning and blasting treatment, after being mixed, metallic aluminium powder, graphite powder and bonding agent add the rubber mold frock in cylinder, again by waiting interior platen press of static pressure that powder is compressing at cylinder inwall, after having suppressed by sample in 200 ℃ of bakings 4 hours, finally in inertia or vacuum atmosphere, in 500 ℃ of heat treatments 2 hours, obtain goods.Metallic aluminium particle 3 in prepared aluminium carbon composite forms the main body framework of composite material; Carbon materials in this composite material forms the conductive network 4(that is interconnected as shown in Figure 2).This aluminium carbon composite has the performance of excellent anti-liquid sulfur and sodium polysulfide corrosion, and at material internal, forms the graphite network being interconnected, and has good conductivity simultaneously.
Embodiment 2
A kind of anodal container of sodium-sulphur battery, comprise the shell of tank 1 that metal is made, shell 1 is mild steel making, the inwall of shell of tank prepare one deck continuously, equal liners 2 of even seamless aluminium carbon composite, this aluminium carbon composite is containing metallic aluminium powder, the carbon materials of 30wt.%, wherein the bonding agent carbon of graphite powder (being carbon dust) 15wt.% and 15wt.% of 70wt.%.Its preparation method is: get the low-carbon (LC) steel cylinder (concrete size is determined according to battery capacity size) of remaining silent in end opening, an one end, low-carbon (LC) steel cylinder inwall is first through cleaning and blasting treatment, metallic aluminium powder, carbon black and bonding agent are mixed, and add absolute ethyl alcohol as diluent, said mixture is sprayed to low-carbon (LC) steel cylinder inwall, after spraying by sample in 60 ℃ of oven dry, again by sample in 200 ℃ of bakings 4 hours, finally in inertia or vacuum atmosphere, in 500 ℃ of heat treatments 2 hours, obtain goods.Metallic aluminium particle 3 in prepared aluminium carbon composite forms the main body framework of composite material; Carbon materials in this composite material forms the conductive network 4(that is interconnected as shown in Figure 2).This aluminium carbon composite has the performance of excellent anti-liquid sulfur and sodium polysulfide corrosion, and at material internal, forms the graphite network being interconnected, and has good conductivity simultaneously.
A kind of anodal container of sodium-sulphur battery, comprise the shell of tank 1 that metal is made, shell 1 is stainless steel making, at the inwall of shell of tank, prepare one deck continuous, all liners 2 of even seamless aluminium carbon composite, this aluminium carbon composite is containing the metallic aluminium powder of 80wt.% and 20% carbon black (being carbon dust), its preparation method is: get an end opening, the stainless steel cylinder (concrete size is determined according to battery capacity size) of remaining silent in one end, stainless steel cylinder inwall is first through cleaning and blasting treatment, after being mixed, metallic aluminium powder and carbon black add the metal die frock in cylinder, then in inert atmosphere in 590 ℃ of temperature, under pressure 30MPa, hot pressing obtains goods for 1 hour.Metallic aluminium particle 3 in prepared aluminium carbon composite forms the main body framework of composite material; Carbon materials in this composite material forms the conductive network 4(that is interconnected as shown in Figure 2).This aluminium carbon composite has the performance of excellent anti-liquid sulfur and sodium polysulfide corrosion, and at material internal, forms the graphite network being interconnected, and has good conductivity simultaneously.
Claims (5)
1. an anodal container for sodium-sulphur battery, comprises the shell of tank that metal is made, and it is characterized in that: the inwall of described shell of tank is prepared the liner of the continuous aluminium carbon composite of one deck.
2. the anodal container of a kind of sodium-sulphur battery according to claim 1, is characterized in that: described shell of tank is the tubular structure of an end opening, other end sealing, and described shell of tank is the one in aluminium, aluminium alloy, mild steel and stainless steel.
3. the anodal container of a kind of sodium-sulphur battery according to claim 1, is characterized in that: described aluminium carbon composite comprises metallic aluminium powder and carbon materials, and wherein metallic aluminium powder is 30～90wt.%, and all the other are carbon materials.
4. the anodal container of a kind of sodium-sulphur battery according to claim 3, is characterized in that: described carbon materials comprises carbon dust and bonding agent carbon, 50～100wt.% that wherein carbon dust is carbon materials, and all the other are bonding agent carbon.
5. according to the anodal container of a kind of sodium-sulphur battery described in claim 1-4, it is characterized in that: the metallic aluminium particle in the liner of described aluminium carbon composite forms the main body framework of composite material, and described carbon materials forms the conductive network being interconnected.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310669116.XA CN103746147B (en) | 2013-12-11 | 2013-12-11 | A kind of positive pole container of sodium-sulphur battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310669116.XA CN103746147B (en) | 2013-12-11 | 2013-12-11 | A kind of positive pole container of sodium-sulphur battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103746147A true CN103746147A (en) | 2014-04-23 |
| CN103746147B CN103746147B (en) | 2016-02-03 |
Family
ID=50503152
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310669116.XA Active CN103746147B (en) | 2013-12-11 | 2013-12-11 | A kind of positive pole container of sodium-sulphur battery |
Country Status (1)
| Country | Link |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106129490A (en) * | 2016-08-17 | 2016-11-16 | 上海电气钠硫储能技术有限公司 | A kind of sodium-sulphur battery electrolyte ceramics pipe closed end protection structure and sodium-sulphur battery |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07302611A (en) * | 1994-05-10 | 1995-11-14 | Hitachi Ltd | High temperature secondary battery |
| JPH1046276A (en) * | 1996-07-31 | 1998-02-17 | Mitsubishi Materials Corp | Positive electrode casing material for sodium-sulfur battery, and positive electrode casing |
| JP2002008713A (en) * | 2000-06-22 | 2002-01-11 | Hitachi Ltd | Sodium-sulfur battery |
| CN202423468U (en) * | 2011-12-16 | 2012-09-05 | 日本碍子株式会社 | Anode container and sodium-sulfur battery |
-
2013
- 2013-12-11 CN CN201310669116.XA patent/CN103746147B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07302611A (en) * | 1994-05-10 | 1995-11-14 | Hitachi Ltd | High temperature secondary battery |
| JPH1046276A (en) * | 1996-07-31 | 1998-02-17 | Mitsubishi Materials Corp | Positive electrode casing material for sodium-sulfur battery, and positive electrode casing |
| JP2002008713A (en) * | 2000-06-22 | 2002-01-11 | Hitachi Ltd | Sodium-sulfur battery |
| CN202423468U (en) * | 2011-12-16 | 2012-09-05 | 日本碍子株式会社 | Anode container and sodium-sulfur battery |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106129490A (en) * | 2016-08-17 | 2016-11-16 | 上海电气钠硫储能技术有限公司 | A kind of sodium-sulphur battery electrolyte ceramics pipe closed end protection structure and sodium-sulphur battery |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103746147B (en) | 2016-02-03 |
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Effective date of registration: 20180426 Address after: 610000 18 West core road, hi-tech West District, Chengdu, Sichuan Patentee after: Dongfang Electric Co., Ltd. Address before: 610036 Shu Han Road, Jinniu District, Chengdu, Sichuan Province, No. 333 Patentee before: Dongfang Electric Corporation |
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